Hydrophobically modified polyethylenimines and polyvinylamines for wrinkle-resistant finishing of textiles containing cellulose

ABSTRACT

A process for wrinkleproofing cellulosic textiles comprises treating the textiles with a finish and drying the treated textiles, wherein the finish comprises one or more water-soluble or water-dispersible hydrophobically modified polyethyleneimines and/or polyvinylamines.  
     Suitable hydrophobically modified polyethyleneimines are hydrophobically modified homopolymers of ethyleneimine, hydrophobically modified graft polymers of polyamidoamines or of polyvinylamines. Suitable hydrophobically modified polyvinylamines are hydrophobically modified at least partially hydrolyzed homo- or copolymers of N-vinylcarboxamides. The polyethyleneimines and polyvinylamines can be crosslinked by polyfunctional crosslinking compounds, quaternized and/or modified by reaction with alkylene oxides, dialkyl carbonates, alkylene carbonates and/or C 1 -C 4 -carboxylic acids.  
     Suitable hydrophobicizing reagents are selected from the group consisting of long-chain linear or branched linear carboxylic acids, linear or branched alkyl halides, alkyl epoxides, alkylketene dimers, cyclic dicarboxylic anhydrides, alkyl isocyanates and chloroformic esters of fatty alcohols.

[0001] This invention relates to processes for wrinkleproofingcellulosic textiles, the use of hydrophobically modifiedpolyethyleneimines and polyvinylamines as antiwrinkle additives and alsotextile treatment compositions, solid and liquid laundry detergentcompositions and laundry conditioning rinse compositions comprising thehydrophobically modified polyethyleneimines and polyvinylamines.

[0002] Cellulosic textiles are given easy care properties for example bytreatment with condensation products of urea, glyoxal and formaldehyde.The finish is applied during the manufacture of textile materials.Softening compounds are frequently further applied with the finish. Thusfinished textiles are less wrinkled and creased, easier to iron andsofter and smoother after laundering compared with untreated cellulosetextiles.

[0003] WO 92/01773 discloses the use of microemulsified aminosiloxanesin fabric conditioners to reduce wrinkling and creasing during thelaundering process. In addition, the use of aminosiloxanes is said tofacilitate ironing.

[0004] WO 98/4772 discloses a process for pretreating textile materialsby applying a mixture of a polycarboxylic acid and a cationic softenerto the textile materials. Wrinkle control is obtained as a result.

[0005] EP-A 0 300 525 discloses fabric conditioners based oncrosslinkable amino-functionalized silicones that impart wrinkle controlor an easy-iron effect to textiles treated therewith.

[0006] WO 99/55953 discloses fabric wrinkle control compositions. Theycomprise lubricants, shape retention polymers, lithium salts andoptionally further ingredients such as softeners, ionic and nonionicsurfactants, odor control agents and bactericides. The formulation ispreferably applied to the textile material by spraying.

[0007] EP-A 0 978 556 describes a mixture of a softener and crosslinkercomponent having cationic properties as a fabric wrinkle and creasecontrol composition and also a method of wrinkleproofing textiles.

[0008] WO 00/24853 describes a fabric softening formulation whichprovides wrinkle reducing benefits to the treated textiles. The wrinklereducing agents used are preferably modified silicones such asaminopolydimethylsiloxane-polyalkylene oxide copolymers or sulfated orsulfonated vegetable oils such as sulfated castor oil.

[0009] It is an object of the present invention to provide a furtherprocess for wrinkleproofing cellulosic textiles and also furtherfinishes for wrinkleproofing such textiles.

[0010] We have found that this object is achieved by a process forwrinkleproofing cellulosic textiles by treating the textiles with afinish and drying the treated textiles, wherein the finish comprises oneor more water-soluble or water-dispersible hydrophobically modifiedpolyethyleneimines and/or polyvinylamines.

[0011] The invention also provides a wrinkleproofing finish forcellulosic textiles that comprises hydrophobically modifiedpolyethyleneimines and/or hydrophobically modified polyvinylamines.

Polyethyleneimines

[0012] Polyethyleneimines which, according to the invention, are usefulas antiwrinkle additives in hydrophobically modified form include forthe purposes of the present invention the homopolymers of ethyleneimine(aziridine) or its higher homologues and also the graft polymers ofpolyamidoamines or polyvinylamines with ethyleneimine or its higherhomologues. The polyethyleneimines can be crosslinked or uncrosslinked,quaternized and/or modified by reaction with alkylene oxides, dialkyl oralkylene carbonates or C1- to C4-carboxylic acids.

[0013] A Homopolymers of Ethyleneimine (Aziridine)

[0014] Useful polyethyleneimines for hydrophobic modification includepolyethyleneimine homopolymers, which can be used in crosslinked oruncrosslinked form. Polyethyleneimine homopolymers are preparableaccording to known processes, for example Römpps Chemie Lexikon, 8thedition 1992, pages 3532-3533, or in Ullmann's Enzyklopädie der

[0015] Technischen Chemie, 4th edition 1974, Volume 8, pages 212-213 andthe references cited therein. They have a molecular weight in the rangefrom about 200 to 1 000 000 g/mol. Higher molecular weight polymers areobtained by crosslinking with polyfunctional compounds.

[0016] Useful polyfunctional crosslinking compounds includediisocyanates such as hexamethylene diisocyanate, isophoronediisocyanate, dicyclohexylmethane 4,4′-diisocyanate and diphenylmethanediisocyanate, dihaloalkanes such as 1,2-dichloroethane,1,3-dichloropropane, 1,4-dichlorobutane and 1,6-dichlorohexane,diepoxides such as oligo- and polyethylene glycol bisepoxides,epihalohydrins such as epichlorohydrin, bischlorohydrin ethers ofalkylene glycols and polyalkylene glycols with 2 to 100 ethylene oxidesand/or propylene oxide units, alkylene carbonates such as ethylenecarbonate and propylene carbonate and bischloroformates such as2,2-dimethylpropylene bischloroformate.

[0017] B Graft Polymers of Polyamidoamines with Ethyleneimine

[0018] Polyethyleneimines for the purposes of the present inventionfurther include ethyleneimine polymers obtainable by graftingpolyamidoamines with ethyleneimine. These can be crosslinked by thecrosslinkers mentioned under A.

[0019] Grafted polyamidoamines are known for example from U.S. Pat. No.4,144,123 or DE-B-24 34 816. The polyamidoamines are obtainable forexample by condensation of

[0020] (i) polyalkylenepolyamines, which can be present in a mixturewith diamines, with

[0021] (ii) at least dibasic carboxylic acids such as oxalic acid,malonic acid, succinic acid, maleic acid, fumaric acid, itaconic acid,adipic acid, tartaric acid, citric acid, propanetricarboxylic acid,butanetetracarboxylic acid, glutaric acid, suberic acid, sebacic acid,terephthalic acid and esters thereof, acyl chlorides or anhydrides whichcan be present in a mixture with up to 50 mol % of monobasic aminoacids, monobasic hydroxycarboxylic acids and/or monobasic carboxylicacids,

[0022] in a molar ratio of (i) to (ii) of 1:0.5 to 1:2.

[0023] Polyalkylenepolyamines are compounds containing at least 3 basicnitrogen atoms in the molecule, for example diethylenetriamine,dipropylenetriamine, triethylenetetramine, tripropylenetetramine,tetraethylenepentamine, pentaethylenehexamine,N-(2-aminoethyl)-1,3-propanediamine andN,N′-bis(3-aminopropyl)ethylenediamine.

[0024] Useful diamines include for example 1,2-diaminoethane,1,3-diaminopropane, 1,4-diamino-butane, 1,6-diaminohexane,1,8-diaminooctane, isophoronediamine, 4,4′-diaminodiphenyl-methane,1,4-bis(3-aminopropyl)piperazine, 4,9-dioxadodecane-1,12-diamine,4,7,10-tri-oxatridecane-1,13-diamine or a,z-diamino compounds ofpolyalkylene oxides.

[0025] The condensation of the compounds (i) and (ii) is effected asdescribed in EP-B 0 703 972 for example.

[0026] The graft polymers generally contain from 10 to 90% by weight ofpolyamidoamines as a grafting base and from 90 to 10% by weight ofethyleneimine as a graft.

[0027] C Graft Polymers of Polyvinylamines with Ethyleneimine

[0028] Useful polyethyleneimines for the purposes of the presentinvention also include ethyleneimine polymers obtainable by graftingpolyvinylamines with ethyleneimine. Polyvinylamines are obtainable bypartial or complete hydrolysis of polymers of open-chainN-vinylcarboxamides of the general formula (I)

[0029] where R1 and R2 are each H or C1- to C6-alkyl,

[0030] and are more particularly described under E and F (seehereinbelow). The degree of hydrolysis is generally in the range from 5to 100%. The graft polymers can be crosslinked by the crosslinkersmentioned under A.

[0031] The graft polymers generally contain from 10 to 90% by weight ofpolyvinylamines as a grafting base and from 90 to 10% by weight ofethyleneimine as a graft.

[0032] D Polyalkyleneimines

[0033] Polyethyleneimines useful for the purposes of the presentinvention also include the polymers of higher homologues ofethyleneimine which correspond to the compounds mentioned under A to C,such as propyleneimine (2-methylaziridine), 1- or 2-butyleneimine(2-ethylaziridine or 2,3-dimethylaziridine). However, the polymers ofethyleneimine are preferred.

[0034] The polyethyleneimines mentioned under A to D may be modified byreaction with alkylene oxides such as ethylene oxide, propylene oxide orbutylene oxide, dialkyl carbonates such as dimethyl carbonate anddiethyl carbonate, alkylene carbonates such as ethylene carbonate orpropylene carbonate, or C1-C4-carboxylic acids. The modification can beeffected before or after the hydrophobicizing step (see hereinbelow).

[0035] The polyethyleneimines or polyvinylamines mentioned under A to Dmay also be present in quaternized form. Useful quaternizing agentsinclude alkylating agents such as dimethyl sulfate, diethyl sulfate,methyl chloride, methyl iodide, ethyl chloride or benzyl chloride. Thequaternization can be effected before or after the hydrophobicizing step(see hereinbelow).

[0036] Polyvinylamines

[0037] Polyvinylamines which, according to the invention, are useful asantiwrinkle additives in hydrophobically modified form include for thepurposes of the present invention the homo- or copolymers ofN-vinylcarboxamides, which are at least partially hydrolyzed. Thepolyvinylamines can be crosslinked or uncrosslinked, quaternized and/ormodified by reaction with alkylene oxides, dialkyl or alkylenecarbonates or C1- to C4-carboxylic acids.

[0038] E At Least Partially Hydrolyzed N-vinylcarboxamide Homopolymers

[0039] They are prepared for example from open-chain N-vinylcarboxamidesof the above formula (I). Useful monomers include for exampleN-vinylformamide (R1=R2=H in the formula I), N-vinyl-N-methylformamide(R1=methyl, R2=H in the formula I), N-vinylacetamide (R1=H, R2=methyl inthe formula I), N-vinyl-N-methylacetamide, (R1=R2=methyl in the formulaI) and N-vinyl-N-ethylacetamide (R1=ethyl, R2=methyl in the formula I).N-Vinylformamide is preferred.

[0040] F At Least Partially Hydrolyzed N-vinylcarboxamide Copolymers

[0041] Polyvinylamines for the purposes of the invention also includecopolymers of

[0042] (a) from 0.1 to 100 mol % of N-vinylcarboxamides of the formula Iand

[0043] (b) from 0 to 99.9 mol % of vinyl formate, vinyl acetate, vinylpropionate, vinyl alcohol, N-vinylurea, N-vinylpyrrolidone,N-vinylpiperidone, N-vinylcaprolactam, N,N-divinylethyleneurea and/orN-vinylimidazole,

[0044] (a) and (b) adding up to 100 mol %, which are at least partiallyhydrolyzed.

[0045] The polymers have a K value of from 5 to 300 (determinedaccording to H. Fikentscher, Cellulose Chemie, Volume 13, pages 58-64and 71-74 (1932), in 5% by weight aqueous sodium chloride solution at25° C. and a polymer concentration of 0.5% by weight). UsefulN-vinylcarboxamides include the compounds mentioned under E.N-Vinylformamide is preferred.

[0046] The polymers mentioned under E and F are at least partiallyhydrolyzed, i.e., the amide groups originally present in the polymershave been converted into amino groups by hydrolysis to an extent in therange from 5 to 100%, preferably in the range from 20 to 100% andparticularly preferably in the range from 40 to 100%. The hydrolysis canbe effected not only in an alkaline but also in an acidic medium.

[0047] The vinylamine polymers and copolymers used according to theinvention are prepared according to processes known for example fromU.S. Pat. No. 4,421,602, EP-A-02 16 387 and EP-A-0 251 182.

[0048] The polyvinylamines mentioned under E and F may also becrosslinked. Useful crosslinkers include the crosslinkers mentionedunder A.

[0049] The polyvinylamines mentioned under E and F may be modified byreaction with alkylene oxides such as ethylene oxide, propylene oxide orbutylene oxide, dialkyl carbonates such as dimethyl carbonate anddiethyl carbonate, alkylene carbonates such as ethylene carbonate orpropylene carbonate or C1-C4-carboxylic acids. The modification can beeffected before or after the hydrophobicizing step (see hereinbelow).

[0050] The polyvinylamines mentioned under E and F may also be presentin quaternized form. Suitable quaternizing agents include alkylatingagents such as dimethyl sulfate, diethyl sulfate, methyl chloride,methyl iodide, ethyl chloride or benzyl chloride. A quaternization canbe effected before or after the hydrophobicizing step (see hereinbelow).

[0051] Hydrophobic Modification

[0052] The polyethyleneimines A to D and polyvinylamines E and F usedaccording to the invention are hydrophobically modified. Hydrophobicallymodified for the purposes of the present invention means that, in thepolymers recited under A to F, the hydrogen atoms of the primary andsecondary amino groups are at least partially replaced by linear orbranched alkyl, alkenyl, hydroxyalkyl or alkylcarboxy radicals having 10to 22 carbon atoms and preferably 14 to 18 carbon atoms in the alkylradical, which may carry further substituents such as carboxyl groups.

[0053] The polymers described above under A to F are hydrophobicallymodified by reaction with

[0054] long-chain linear or branched carboxylic acids having 10 to 22carbon atoms and preferably 14 to 18 carbon atoms in the alkyl oralkylene radical, such as capric acid, undecanoic acid, lauric acid,tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid,margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenicacid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid,arachidonic acid and mixtures thereof, preferably stearic acid, palmiticacid and oleic acid, or the acyl chlorides, esters or anhydrides of thecarboxylic acids mentioned,

[0055] linear or branched alkyl halides having 10 to 22 carbon atoms andpreferably 14 to 18 carbon atoms in the alkyl radical, such astetradecyl chloride, hexadecyl chloride, octadecyl chloride and mixturesthereof,

[0056] alkyl epoxides having 10 to 22 carbon atoms and preferably 14 to18 carbon atoms, such as hexadecenyl oxide and octadecenyl oxide andmixtures thereof,

[0057] alkylketene dimers having 10 to 22 carbon atoms and preferably 14to 18 carbon atoms in the alkyl radical, such as laurylketene,palmitylketene, stearylketene and oleylketene dimers and mixturesthereof,

[0058] cyclic dicarboxylic anhydrides, especially alkyl-substitutedsuccinic anhydrides having 10 to 22 carbon atoms and preferably 14 to 18carbon atoms in the alkyl radical, such as dodecenylsuccinic anhydride,tetradecylsuccinic anhydride, hexadecenylsuccinic anhydride and mixturesthereof,

[0059] alkyl isocyanates having 10 to 22 carbon atoms and preferably 14to 18 carbon atoms in the alkyl radical, such as tetradecyl isocyanate,hexadecyl isocyanate, octadecyl isocyanate and mixtures thereof, or

[0060] chloroformic esters of fatty alcohols having 10 to 22 carbonatoms and preferably 14 to 18 carbon atoms.

[0061] The degree of hydrophobicization is in the range from 0.1 to 20%by weight, preferably in the range from 0.3 to 10% by weight,particularly preferably in the range from 0.5 to 7% by weight of theabovementioned hydrophobicization reagents, based on the weight of theready-prepared product.

[0062] The invention also provides for the use of the hydrophobicallymodified polyethyleneimines and polyvinylamines in finishes forwrinkleproofing cellulosic textiles. Finishes are any liquidformulations which contain the hydrophobically modifiedpolyethyleneimines or polyvinylamines in dissolved or dispersed form forapplication to the textile material. The finishes of the invention canbe present for example as finishes in the narrower sense in themanufacture of textiles or in the form of an aqueous washing liquor oras a liquid textile treatment composition. Useful solvents include forexample water, alcohols such as methanol, ethanol and propanol, THF ormixtures thereof. It is possible for example to treat textiles with thefinish in the course of their manufacture. Textiles which have not beenadequately finished, if at all, may be treated with a textile treatmentcomposition which contains the hydrophobically modifiedpolyethyleneimines or polyvinylamines, for example before or after homelaundering, for example during ironing. But it is also possible to treatthe textiles with hydrophobically modified polyethyleneimines orpolyvinylamines in the main wash cycle or after the main wash cycle inthe conditioning or softening rinse cycle of the washing machine.

[0063] The present invention also provides for the use of thehydrophobically modified polyethyleneimines and polyvinylamines in themanufacture of textiles, in the treatment of textiles before or afterlaundering, in the laundry main wash cycle, in the laundry rinse cycleand during ironing. Different formulations are needed in each case.

[0064] The treatment before or after laundering may utilize a textiletreatment composition which, as well as hydrophobically modifiedpolyethyleneimines or polyvinylamines in dissolved or dispersed form,contains a surfactant. In this treatment, the cellulosic textiles arefor example sprayed with the hydrophobically modified polyethyleneiminesor polyvinylamines with an add-on which is generally in the range from0.01 to 10% by weight, preferably in the range from 0.1 to 7% by weightand particularly preferably in the range from 0.3 to 4% by weight, basedon the weight of the dry textile material. But the finish may also beapplied to the textile material by dipping the textiles into a bathwhich contains generally from 0.1 to 10% by weight and preferably from0.3 to 5% by weight, based on the weight of the dry textile material, ofhydrophobically modified polyethyleneimines or polyvinylamines indissolved or dispersed form. The textile material is either dipped onlybriefly into the bath or else allowed to dwell therein for a period offrom 1 to 30 min for example.

[0065] Cellulosic textiles which have been treated with the finisheither by spraying or by dipping are if necessary squeezed off anddried. Drying may take place in air or else in a dryer or else bysubjecting the treated textile material to hot ironing. The finishbecomes fixed on the textile material in the course of drying. The bestconditions in each case are readily ascertainable by experimentation.The temperatures for drying, including ironing, are for example in therange from 40 to 150° C. and preferably in the range from 60 to 110° C.For ironing, the cotton program of the iron is suitable in particular.Textiles treated with the hydrophobically modified polyethyleneimines orpolyvinylamines in dissolved or dispersed form according to theabove-described process exhibit an excellent level of wrinkle and creaseresistance that is durable to multiple laundering. There is frequentlyno longer any need to iron the textiles. The textiles thus treatedadditionally possess fiber and color protection.

[0066] The invention also provides a textile treatment compositioncomprising

[0067] a) from 0.1 to 40% by weight and preferably from 0.5 to 25% byweight of at least one hydrophobically modified polyethyleneimine and/orpolyvinylamine,

[0068] b) from 0 to 30% by weight of one or more silicones,

[0069] c) from 0 to 30% by weight of one or more cationic and/ornonionic surfactants,

[0070] d) from 0 to 60% by weight of further ingredients such as furtherwetting agents, softeners, lubricants, water-soluble, film-forming andadhesive polymers, scents, colorants, stabilizers, fiber and colorprotection additives, viscosity modifiers, soil release additives,corrosion control additives, bactericides, preservatives and sprayingassistants, and

[0071] e) from 0 to 99.9% by weight of water,

[0072] the components a) to e) adding up to 100% by weight.

[0073] Preferred silicones b) are amino-containing silicones, which arepreferably present in microemulsified form, alkoxylated, especiallyethoxylated, silicones, polyalkylene oxide-polysiloxanes, polyalkyleneoxide-aminopolydimethylsiloxanes, silicones having quaternary ammoniumgroups (silicone quats) and silicone surfactants.

[0074] Useful softeners or lubricants include for example oxidizedpolyethylenes or paraffinic waxes and oils. Useful water-soluble,film-forming and adhesive polymers include for example (co)polymersbased on acrylamide, N-vinylpyrrolidone, vinylformamide,N-vinylimidazole, vinylamine, N,N′-dialkylaminoalkyl (meth)acrylates,N,N′-dialkylaminoalkyl(meth)acrylamides, (meth)acrylic acid, alkyl(meth)acrylates and/or vinylsulfonate. The aforementioned basic monomersmay also be used in quaternized form.

[0075] A textile pretreatment formulation to be applied to the textilematerial by spraying may additionally include a spraying assistant. Insome cases, it can also be of advantage to include in the formulationalcohols such as ethanol, isopropanol, ethylene glycol or propyleneglycol. Further customary additives are scents, colorants, stabilizers,fiber and color protection additives, viscosity modifiers, soil releaseadditives, corrosion control additives, bactericides and preservativesin customary amounts.

[0076] The textile treatment composition may generally also be appliedby spraying in the course of ironing after laundering. This not onlysubstantially facilitates ironing, but also imparts sustained wrinkleand crease resistance to the textiles.

[0077] The hydrophobically modified polyethyleneimines andpolyvinylamines may also be used when the textiles are washed in themain wash cycle of the washing machine.

[0078] The invention further provides a solid laundry detergentcomposition comprising

[0079] a) from 0.05 to 20% by weight of at least one hydrophobicallymodified polyethyleneimine and/or polyvinylamine,

[0080] b) from 0 to 20% by weight of one or more silicones,

[0081] c) from 0.1 to 40% by weight of at least one nonionic and/oranionic surfactant,

[0082] d) from 0 to 50% by weight of one or more inorganic builders,

[0083] e) from 0 to 10% by weight of one or more organic cobuilders,

[0084] f) from 0 to 60% by weight of other customary ingredients such asstandardizers, enzymes, perfume, complexing agents, corrosioninhibitors, bleaches, bleach activators, cationic surfactants, bleachcatalysts, dye transfer inhibitors, antiredeposition agents, soilrelease polyesters, colorants, bactericides, dissolution improversand/or disintegrants,

[0085] components a) to f) adding up to 100% by weight.

[0086] A solid laundry detergent formulation according to the inventionis customarily present in powder, granule, extrudate or tablet form.

[0087] The invention further provides a liquid laundry detergentcomposition comprising

[0088] a) from 0.05 to 20% by weight of at least one hydrophobicallymodified polyethyleneimine and/or polyvinylamine,

[0089] b) from 0 to 20% by weight of one or more silicones,

[0090] c) from 0.1 to 40% by weight of at least one nonionic and/oranionic surfactant,

[0091] d) from 0 to 20% by weight of one or more inorganic builders,

[0092] e) from 0 to 10% by weight of one or more organic cobuilders,

[0093] f) from 0 to 60% by weight of other customary ingredients such assodium carbonate, enzymes, perfume, complexing agents, corrosioninhibitors, bleaches, bleach activators, bleach catalysts, cationicsurfactants, dye transfer inhibitors, antiredeposition agents, soilrelease polyesters, colorants, bactericides, nonaqueous solvents,solubilizers, hydrotropes, thickeners and/or alkanolamines,

[0094] g) from 0 to 99.85% by weight of water,

[0095] components a) to g) adding up to 100% by weight.

[0096] Useful silicones b) include the abovementioned silicones.

[0097] Useful anionic surfactants c) are in particular:

[0098] (fatty) alcohol sulfates of (fatty) alcohols having from 8 to 22,preferably from 10 to 18, carbon atoms, for example C9- to C1 -alcoholsulfates, C12- to C14-alcohol sulfates, C12- to C18-alcohol sulfates,lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate,stearyl sulfate and tallow fatty alcohol sulfate;

[0099] sulfated alkoxylated C8- to C22-alcohols (alkyl ether sulfates).Compounds of this kind are prepared for example by first alkoxylating aC8- to C22-alcohol, preferably a C10- to C18-alcohol, for example afatty alcohol, and then sulfating the alkoxylation product. Thealkoxylation is preferably carried out using ethylene oxide;

[0100] linear C8- to C20-alkylbenzenesulfonates (LAS), preferably linearC9- to C13-alkylbenzenesulfonates and -alkyltoluenesulfonates,

[0101] alkanesulfonates such as C8- to C24-alkanesulfonates, preferablyC10- to C18-alkanesulfonates;

[0102] soaps such as, for example, the sodium and potassium salts of C8-to C24-carboxylic acids.

[0103] The anionic surfactants mentioned are preferably included in thelaundry detergent in the form of salts. Suitable cations in these saltsare alkali metal ions such as sodium, potassium and lithium and ammoniumions such as hydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium.

[0104] Useful nonionic surfactants c) are in particular:

[0105] alkoxylated C8- to C22-alcohols such as fatty alcohol alkoxylatesor oxo alcohol alkoxylates. These may have been alkoxylated withethylene oxide, propylene oxide and/or butylene oxide. Usefulsurfactants here include all alkoxylated alcohols which contain at leasttwo molecules of one of the aforementioned alkylene oxides. Here it ispossible to use block polymers of ethylene oxide, propylene oxide and/orbutylene oxide or addition products which contain the aforementionedalkylene oxides in random distribution. Nonionic surfactants generallycontain from 2 to 50, preferably from 3 to 20, mol of at least onealkylene oxide per mole of alcohol. The alkylene oxide component ispreferably ethylene oxide. The alcohols preferably have from 10 to 18carbon atoms. Depending on the type of alkoxylation catalyst used tomake them, alkoxylates have a broad or narrow alkylene oxide homologdistribution;

[0106] alkylphenol alkoxylates such as alkylphenol ethoxylates havingC6- to C14-alkyl chains and from 5 to 30 alkylene oxide units;

[0107] alkylpolyglucosides having from 8 to 22, preferably from 10 to18, carbon atoms in the alkyl chain and generally from 1 to 20,preferably from 1.1 to 5, glucoside units;

[0108] N-alkylglucamides, fatty acid amide alkoxylates, fatty acidalkanolamide alkoxylates and also block copolymers of ethylene oxide,propylene oxide and/or butylene oxide.

[0109] Useful inorganic builders d) are in particular:

[0110] crystalline or amorphous aluminosilicates having ion-exchangingproperties such as zeolites in particular. Useful zeolites include inparticular zeolites A, X, B, P, MAP and HS in their sodium form or informs in which sodium has been partly replaced by other cations such aslithium, potassium, calcium, magnesium or ammonium;

[0111] crystalline silicates such as in particular disilicates orsheet-silicates, for example δ-Na2Si205 or β-Na2Si205. Silicates can beused in the form of their alkali metal, alkaline earth metal or ammoniumsalts, preferably as sodium, lithium and magnesium silicates;

[0112] amorphous silicates such as for example sodium metasilicate oramorphous disilicate;

[0113] carbonates and bicarbonates. These can be used in the form oftheir alkali metal, alkaline earth metal or ammonium salts. Preferenceis given to sodium, lithium and magnesium carbonates or bicarbonates,especially sodium carbonate and/or sodium bicarbonate;

[0114] polyphosphates such as for example pentasodium triphosphate.

[0115] Useful organic cobuilders e) include in particular low molecularweight, oligomeric or polymeric carboxylic acids.

[0116] Useful low molecular weight carboxylic acids include for examplecitric acid, hydrophobically modified citric acid such as for exampleagaric acid, malic acid, tartaric acid, gluconic acid, glutaric acid,succinic acid, imidodisuccinic acid, oxydisuccinic acid,propanetricarboxylic acid, butanetetracarboxylic acid,cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids andaminopoly-carboxylic acids such as for example nitrilotriacetic acid,β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediaceticacid, isoserinediacetic acid, N-(2-hydroxyethyl)iminodiacetic acid,ethylenediaminedisuccinic acid and methyl- and ethylglycinediaceticacid;

[0117] useful oligomeric or polymeric carboxylic acids include forexample homopolymers of acrylic acid, oligomaleic acids, copolymers ofmaleic acid with acrylic acid, methacrylic acid, C2-C22-olefins such asfor example isobutene or long-chain α-olefins, vinyl alkyl ethers havingC1-C8-alkyl groups, vinyl acetate, vinyl propionate, (meth)acrylicesters of C1- C8-alcohols and styrene. Preference is given to using thehomopolymers of acrylic acid and copolymers of acrylic acid with maleicacid. Polyaspartic acids are also useful as organic cobuilders.Oligomeric and polymeric carboxylic acids are used in acid form or assodium salt.

[0118] Useful bleaches include for example adducts of hydrogen peroxidewith inorganic salts such as sodium perborate monohydrate, sodiumperborate tetrahydrate or sodium carbonate perhydrate or percarboxylicacids such as phthalimidopercaproic acid.

[0119] Useful bleach activators include for exampleN,N,N′,N′-tetraacetylethylenediamine (TAED), sodiump-nonanoyloxybenzenesulfonate or N-methylmorpholinium acetonitrilemethosulfate.

[0120] Preferred enzymes which are used in laundry detergentcompositions are proteases, lipases, amylases, cellulases, oxidases orperoxidases.

[0121] Useful dye transfer inhibitors include for example homo- andcopolymers of 1-vinylpyrrolidone, of 1-vinylimidazole or of4-vinylpyridine N-oxide. Homo- and copolymers of 4-vinylpyridine whichhave been reacted with chloroacetic acid are likewise useful as dyetransfer inhibitors.

[0122] A detailed description of the laundry detergent ingredientsmentioned is found for example in WO 99/06524 or WO 99/04313 and inLiquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67,Marcel Decker, New York, 1997, pp. 272-304.

[0123] The concentration of the hydrophobically modifiedpolyethyleneimines or the polyvinylamines in the wash liquor is forexample in the range from 10 to 5 000 ppm, preferably in the range from50 to 1 000 ppm. Textiles treated with the hydrophilically modifiedpolyethyleneimines or polyvinylamines in the main wash cycle of thewashing machine not only wrinkle substantially less than untreatedtextiles, they are also easier to iron, softer and smoother, moredimensionally and shape stable and, because of their fiber and colorprotection, look less “used”, i.e., exhibit less fluff and fewer knotsand less color damage or fading, after repeated washing.

[0124] The hydrophobically modified polyethyleneimines and/orpolyvinylamines may be used in the rinse or conditioning cycle followingthe main wash cycle. The concentration of the hydrophobically modifiedpolyethyleneimines or the polyvinylamines in the wash liquor is forexample in the range from 10 to 5 000 ppm, preferably in the range from50 to 1 000 ppm. The rinse liquor may if desired include ingredientstypical for a fabric conditioner or refresher. Textiles treated in thisway and then dried on the line or preferably in a tumble dryer likewiseexhibit a very high level of crease resistance that is associated withthe positive effects on ironing that were described above. Creaseresistance can be substantially enhanced by briefly ironing the textilesonce after drying. The treatment in the softening or conditioning rinsecycle also has a favorable effect on the shape retention of thetextiles. It further inhibits the formation of knots and fluff andsuppresses color damage.

[0125] The invention further provides a laundry conditioning rinsecomposition comprising

[0126] a) from 0.05% to 40% by weight of at least one hydrophobicallymodified polyethyleneimine and/or polyvinylamine,

[0127] b) from 0 to 20% by weight of one or more silicones,

[0128] c) from 0.1 to 40% by weight of at least one cationic surfactant,

[0129] d) from 0 to 30% by weight of one or more nonionic surfactants,

[0130] e) from 0 to 30% by weight of further customary ingredients suchas lubricants, wetting agents, film-forming polymers, scents, colorants,stabilizers, fiber and color protection additives, viscosity modifiers,soil release additives, corrosion control additives, bactericides andpreservatives, and

[0131] f) from 0 to 99.85% by weight of water,

[0132] components a) to f) adding up to 100% by weight.

[0133] Preferred silicones b) are the aforementioned silicones.

[0134] Preferred cationic surfactants c) are selected from the group ofthe quaternary diesterammonium salts, the quaternary tetraalkylammoniumsalts, the quaternary diamidoammonium salts, the amidoamine esters andimidazolium salts. These are preferably present in the laundryconditioning rinse compositions in an amount of from 3 to 30% by weight.Examples are quaternary diesterammonium salts which have two C11- toC22-alk(en)ylcarbonyloxy(mono- to pentamethylene) radicals and two C1-to C3-alkyl or -hydroxyalkyl radicals on the quaternary nitrogen atomand, for example, chloride, bromide, methosulfate or sulfate ascounterion.

[0135] Quaternary diesterammonium salts further include in particularthose which have a C1- to C22-alk(en)ylcarbonyloxytrimethylene radicalbearing a C11- to C22-alk(en)ylcarbonyloxy radical on the central carbonatom of the trimethylene group and three C1- to C3-alkyl or-hydroxyalkyl radicals on the quaternary nitrogen atom and, for example,chloride, bromide, methosulfate or sulfate as counterion.

[0136] Quaternary tetraalkylammonium salts are in particular those whichhave two C1- to C6-alkyl radicals and two C8- to C24-alk(en)yl radicalson the quaternary nitrogen atom and, for example, chloride, bromide,methosulfate or sulfate as counterion.

[0137] Quaternary diamidoammonium salts are in particular those whichbear two C8- to C24-alk(en)ylcarbonylaminoethylene radicals, asubstituent selected from hydrogen, methyl, ethyl and polyoxyethylenehaving up to 5 oxyethylene units and as fourth radical a methyl group onthe quaternary nitrogen atom and, for example, chloride, bromide,methosulfate or sulfate as counterion.

[0138] Amidoamino esters are in particular tertiary amines bearing aC11- to C22-alk(en)ylcarbonylamino(mono- to trimethylene) radical, a C1-to C22-alk(en)ylcarbonyloxy(mono- to trimethylene) radical and a methylgroup as substituents on the nitrogen atom.

[0139] Imidazolinium salts are in particular those which bear a C14- toC18-alk(en)yl radical in position 2 of the heterocycle, a C14- toC18-alk(en)ylcarbonyl(oxy or amino)ethylene radical on the neutralnitrogen atom and hydrogen, methyl or ethyl on the nitrogen atomcarrying the positive charge, while counterions here are for examplechloride, bromide, methosulfate or sulfate.

[0140] The examples hereinbelow illustrate the invention.

EXAMPLES

[0141] The percentages in the examples are by weight, unless the contextsuggests otherwise.

Example 1 Amidation of Polyethyleneimine (MW 25 000) with Stearic Acid

[0142] In a 2 1 stirred apparatus equipped with a distillation head, 680g of polyethyleneimine (MW 25 000) were heated to 150° C. undernitrogen. 45 g of stearic acid were added a little at a time. Themixture was then stirred at 180° C. for 24 h while the water of reactionwas distilled off. This provided a highly viscous water-soluble product.

Example 2 Reaction of a Cationic Polymer with Alkylketene Dimer

[0143] 649 g of a 23% by weight aqueous solution of a polymer ofdiethylenetriamine and adipic acid (weight ratio 40:60) which had beengrafted with ethyleneimine (in a weight ratio 1:1) and then crosslinkedwith a polyethylene oxide bischlorohydrin crosslinker (34 ethylene oxideunits, 30% by weight based on the ready-prepared polymer)—total molarmass 2 000 000—were heated to 90° C. This mixture was admixed with asolution of 0.97 g of stearyldiketene (lactone content: 87.8%) in 5 mlof THF. The mixture was subsequently stirred at 90° C. for 3 h. Thesmall amount of THF was distilled off in the process. This provided adispersion having a solids content of 23%.

Example 3 Quaternization of a Polyethyleneimine Modified with StearicAcid

[0144] The amidation of polyethyleneimine (MW 25 000) with stearic acidwas carried out similarly to example 1.

[0145] 4.6 g of the product thus prepared were dissolved in 50 ml oftoluene. 26.7 g of dimethyl sulfate were slowly added dropwise at 100°C. The product was precipitated in the course of the reaction. Themixture was stirred at 100° C. for a further 5 h. Toluene was thendecanted off and the remaining solid residue was thoroughly washed withacetone and dried. This provided a yellowish water-soluble wax.

Example 4 Hydrophobicization of Polyethyleneimine with Stearic Acid andSubsequent Alkoxylation

[0146] The amidation of polyethyleneimine (MW 25 000) with stearic acidwas carried out similarly to example 1.

[0147] 500 g of the product thus prepared were dissolved in 500 g ofwater and heated to 100° C. 433 g of ethylene oxide gas were injected atthis temperature. This provided an aqueous polymer solution having asolids content of 65%.

Example 5 Alkoxylation of Polyethyleneimine and SubsequentHydrophobicization by Esterification with Stearoyl Chloride

[0148] 2.1 kg of a 60% by weight aqueous solution of polyethyleneimine(MW 2 000) were reacted with 1.15 kg of ethylene oxide at 100° C. Thereaction mixture was subsequently admixed at 50° C. with 125 g of a 50%by weight aqueous solution of potassium hydroxide and with 1.15 1 ofxylene. The water was removed with a Dean-Stark apparatus and thereaction mixture was reacted with 7.78 kg of ethylene oxide at 150° C.Xylene was distilled off, the reaction mixture was stripped with steamand the water was removed by distillation.

[0149] 500 g of the water-free product thus obtained were heated to 80°C. 10.0 g of stearoyl chloride were added over 15 min, and the mixturewas subsequently stirred at 80° C. for 2 h. This provided awater-soluble product which was waxy at room temperature.

Example 6 Hydrophobicization of Polyvinylamine with 1,2-octadecylEpoxide and Subsequent Alkoxylation

[0150] 200 g of an 8.6% by weight aqueous polyvinylamine solution (MW 30000, pH 11.9, degree of hydrolysis 98.6%, desalted) were admixed with1.60 g of a melt of octadecyl epoxide. The reaction mixture was stirredat 90° C. for 40 h.

[0151] 100 g of the above reaction solution were reacted with 26.0 g ofbutylene oxide at 90° C. After cooling to 50° C., 1.7 g of a 50% byweight aqueous solution of potassium hydroxide and 300 g of xylene wereadded, the water was removed using a Dean- Stark apparatus and thereaction mixture was reacted with 34.8 g of ethylene oxide.

[0152] Xylene was distilled off and the reaction mixture wassubsequently stripped with steam. This provided the product as anaqueous solution.

Finishing of Fabric Samples

[0153] The finish used was a 1% by weight aqueous solution or dispersionof the polymers of examples 1 to 6.

[0154] Cotton fabrics having the size quoted in each case in table 1 anda basis weight of 160 g/m2 were sprayed on both sides with the finishesof examples 1-6 so that the add-on was 2%, based on the respectiveweight of the dry textile material, and then while slightly moist ironedhot.

[0155] The fabric samples thus treated and, for comparison, untreatedfabric samples of the same size were washed in the presence of ballastfabric with a liquid detergent at 40° C. in an automatic domesticwashing machine (load in the range from 1.5 to 3.0 kg) and then tumbledried. A standard washing program and a standard drying program(respectively 40° C. colored wash and the cupboard dry program) wereused. After drying, the sheetlike fabric samples were visually rated onthe lines of AATCC test method 124, where a rating of 1 indicates thatthe fabric is highly wrinkled and has many creases and a rating of 5 isawarded to wrinkle- and crease-free fabric. The fabric samplespretreated with the finishes A, B and C received ratings in the rangefrom 2 to 3.5. By contrast, the untreated fabric samples were eachrated 1. TABLE 1 Cotton Cotton Cotton (40 cm × 40 cm) load (40 cm × 40cm) (40 cm × 80 cm) 1.5 kg load 3.0 kg load 1.5 kg untreated 1 1 1 1 3.52.5 2.5 2 3 2 2.5 3 3.5 3 3 4 3 2.5 3 5 2 2 2 6 3 2 2.5

We claim:
 1. The process for wrinkleproofing cellulosic textiles bytreating the textiles with a finish and drying the treated textiles, thefinish comprising one or more water-soluble or water-dispersiblehydrophobically modified polyethyleneimines and/or polyvinylamines. 2.The process of claim 1, wherein the hydrophobically modifiedpolyethyleneimines are hydrophobically modified ethyleneiminehomopolymers which may be crosslinked by polyfunctional crosslinkingcompounds.
 3. The process of claim 1, wherein the hydrophobicallymodified polyethyleneimines are hydrophobically modified graft polymersof polyamidoamines or of polyvinylamines which may be crosslinked bypolyfunctional crosslinking compounds.
 4. The process of claim 1,wherein the hydrophobically modified polyvinylamines are hydrophobicallymodified at least partially hydrolyzed homo- or copolymers ofN-vinylcarboxamides which may be crosslinked by polyfunctionalcrosslinking compounds.
 5. The process of any of claims 1 to 4, whereinthe hydrophobically modified polyethyleneimines or polyvinylamines arequaternized and/or modified by reaction with alkylene oxides, dialkylcarbonates, alkylene carbonates and/or C1-C4-carboxylic acids.
 6. Theprocess of any of claims 1 to 5, wherein the hydrophobically modifiedpolyethyleneimines and polyvinylamines are obtainable by reaction with ahydrophobicizing reagent selected from the group consisting oflong-chain linear or branched carboxylic acids, linear or branched alkylhalides, alkyl epoxides, alkylketene dimers, cyclic dicarboxylicanhydrides, alkyl isocyanates and chloroformic esters of fatty alcohols.7. The process of any of claims 1 to 6, wherein the degree ofhydrophobicization of the hydrophobically modified polyethyleneimines orpolyvinylamines is from 0.1 to 20% by weight of hydrophobicizingreagent, based on the ready-prepared product.
 8. The use ofhydrophobically modified polyethyleneimines or polyvinylamines asdefined in any of claims 1 to 7 for wrinkleproofing cellulosic textiles.9. The use according to claim 8 in textile treatment compositions, solidand liquid laundry detergent compositions and laundry conditioning rinsecompositions.
 10. The use according to claim 8 in textile manufacture,textile treatment, the laundry main wash cycle, the laundry rinse cycleand ironing.
 11. A finish for wrinkleproofing cellulosic textiles,comprising hydrophobically modified polyethyleneimines and/orpolyvinylamines as defined in any of claims 1 to 7, wherein thepolyethyleneimines and polyvinylamines are hydrophobically modified bythe at least partial replacement of the hydrogen of their primary andsecondary amino groups by linear or branched alkyl, alkenyl,hydroxyalkyl or alkylcarboxy radical having 10 to22 carbon atoms.
 12. Atextile treatment composition comprising a) from 0.1 to 40% by weight ofat least one hydrophobically modified polyethyleneimine and/orpolyvinylamine as defined in claim 11, b) from 0 to 30% by weight of oneor more silicones, c) from 0 to 30% by weight of one or more cationicand/or nonionic surfactants, d) from 0 to 60% by weight of furtheringredients such as further wetting agents, softeners, lubricants,water-soluble, film-forming and adhesive polymers, scents, colorants,stabilizers, fiber and color protection additives, viscosity modifiers,soil release additives, corrosion control additives, bactericides,preservatives and spraying assistants, and e) from 0 to 99.9% by weightof water, the components a) to e) adding up to 100% by weight.
 13. Asolid laundry detergent composition comprising a) from 0.05 to 20% byweight of at least one hydrophobically modified polyethyleneimine and/orpolyvinylamine as defined in claim 11, b) from 0 to 20% by weight of oneor more silicones, c) from 0.1 to 40% by weight of at least one nonionicand/or anionic surfactant, d) from 0 to 50% by weight of one or moreinorganic builders, e) from 0 to 10% by weight of one or more organiccobuilders, f) from 0 to 60% by weight of further customary ingredientssuch as standardizers, enzymes, perfume, complexing agents, corrosioninhibitors, bleaches, bleach activators, cationic surfactants, bleachcatalysts, dye transfer inhibitors, antiredeposition agents, soilrelease polyesters, colorants, bactericides, dissolution improversand/or disintegrants, components a) to f) adding up to 100% by weight.14. A liquid laundry detergent composition comprising a) from 0.05 to20% by weight of at least one hydrophobically modified polyethyleneimineand/or polyvinylamine as defined in claim 11, b) from 0 to 20% by weightof one or more silicones, c) from 0.1 to 40% by weight of at least onenonionic and/or anionic surfactant, d) from 0 to 20% by weight of one ormore inorganic builders, e) from 0 to 10% by weight of one or moreorganic cobuilders, f) from 0 to 60% by weight of other customaryingredients such as sodium carbonate, enzymes, perfume, complexingagents, corrosion inhibitors, bleaches, bleach activators, bleachcatalysts, cationic surfactants, dye transfer inhibitors,antiredeposition agents, soil release polyesters, colorants,bactericides, nonaqueous solvents, solubilizers, hydrotropes, thickenersand/or alkanolamines, g) from 0 to 99.85% by weight of water, componentsa) to g) adding up to 100% by weight.
 15. A laundry conditioning rinsecomposition comprising a) from 0.05% to 40% by weight of at least onehydrophobically modified polyethyleneimine and/or polyvinylamine asdefined in claim 11, b) from 0 to 20% by weight of one or moresilicones, c) from 0.1 to 40% by weight of at least one cationicsurfactant, d) from 0 to 30% by weight of one or more nonionicsurfactants, e) from 0 to 30% by weight of further customary ingredientssuch as silicones, other lubricants, wetting agents, film-formingpolymers, scents, colorants, stabilizers, fiber and color protectionadditives, viscosity modifiers, soil release additives, corrosioncontrol additives, bactericides and preservatives, and f) from 0 to99.85% by weight of water, components a) to f) adding up to 100% byweight.